有色金属材料与工程  2026, Vol. 47 Issue (2): 43-58    DOI: 10.13258/j.cnki.nmme.20260109001   PDF    
Al基钎料优化设计与脆性化合物及气孔缺陷生长机制原位研究进展
黄冠1, 杨俊朝1, 路全彬2, 纠永涛4, 郭鹏2, 杨景卫1, 乔健1, 丁宗业2,3    
1. 佛山大学 机电工程与自动化学院,广东 佛山 528225;
2. 中国机械总院集团郑州机械研究所有限公司高性能新型焊接材料全国重点实验室,河南 郑州 450001;
3. 上海交通大学 材料科学与工程学院,上海 200240;
4. 宁波中机松兰刀具科技有限公司,浙江 宁波 315700
摘要:系统综述了Al基钎料的最新研究进展,重点围绕合金成分设计、复合钎料与组织缺陷演化机制的原位研究展开,旨在为成分设计优化与性能调控提供重要参考。在合金成分方面,通过对Al-Si系与Zn-Al系钎料进行成分设计,实现共晶多组元降低熔点、稀土元素细化组织、活性元素增强润湿;在复合钎料技术方面,通过材料与结构创新开发出层状复合钎料及表面镀层、药芯/药皮钎焊丝及膏状复合钎料等新型材料;在脆性化合物与气孔缺陷演化机制方面,阐述了利用同步辐射X射线成像技术深入揭示复杂脆性化合物与氢气孔缺陷的生长与形态演变机制,为有效改善钎料润湿性、抑制脆性相过量生长与缓解接头残余应力提供关键支撑。最后,对Al基钎料的未来发展进行展望,指出AI赋能新型钎料研发、极端条件下钎焊理论的原位研究和发展、钎焊过程自动化与智能化在线控制是应对未来复杂及异质构件高性能连接挑战的方向。
关键词Al钎料    复合钎料    合金成分设计    脆性化合物与氢气孔    原位表征    
Progress in optimization design of Al-based brazing materials with high-performance in-situ research on growth mechanisms of brittle compounds and pore defects
HUANG Guan1, YANG Junchao1, LU Quanbin2, JIU Yongtao4, GUO Peng2, YANG Jingwei1, QIAO Jian1, DING Zongye2,3    
1. School of Mechanical and Electrical Engineering and Automation, Foshan University, Foshan 528225, China;
2. State Key Laboratory of High Performance & Advanced Welding Materials, China Academy of Machinery Zhengzhou Research Institute of Mechanical Engineering Co., Ltd., Zhengzhou 450001, China;
3. School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;
4. Ningbo Zhongji Songlan Cutting Tools Technology Co., LTD., Ningbo 315700, China
Abstract: Aluminum alloy heterogeneous components connected via brazing technology are considered an important development direction in high-end manufacturing due to their good corrosion resistance, excellent thermal and electrical conductivity. However, conventional Al-based brazing fillers face issues such as relatively high melting points, insufficient wettability, and inadequate joint strength, while conventional brazing processes also suffer from challenges like difficulty in controlling brazing filler dosage, susceptibility to moisture absorption leading to failure, environmental pollution, and poor welding consistency. By performing compositional design on Al-Si and Zn-Al brazing fillers through eutectic multi-component systems, rare earth elements, and active elements, it is possible to lower the melting point, refine the microstructure, enhance performance, and improve joint properties. Utilizing composite brazing material forms such as laminated composite brazing materials, surface coatings on base materials, flux-cored and flux-coated brazing materials, and composite brazing pastes can enhance the mechanical properties, reliability, and process stability of brazed joints. Furthermore, the use of synchrotron radiation X-ray imaging technology to reveal the growth and morphological evolution mechanisms of complex brittle compounds and hydrogen porosity defects provides critical support for regulating joint microstructure and performance. Future research should leverage AI to empower the development of new brazing materials, conduct in-situ studies on brazing theory under extreme conditions, and achieve automated, intelligent online control of the brazing process.
Key words: Al brazing materials    composite brazing materials    alloy composition design    brittle compounds and hydrogen pores    in-situ characterization    

随着航空航天、半导体制造、精密光学等领域对材料性能的要求日益提高,单一材料结构已难以满足多元化的服役需求[1]。复杂与异质结构材料通过不同材料的性能互补与协同作用,能够实现单一材料所不具备的多功能特性与优异的综合性能[2],因此,高性能复杂与异质构件已成为高端制造领域的重要发展方向[3]。钎焊技术因其适应性好、结合强度高等优势,已成为实现此类构件连接的一项关键工艺[4],其中,钎料是决定钎焊接头可靠性的核心因素,常用体系主要包括Ni基[5]、Al基[6]、Ag基[7]、Zn基[8]、Sn基[9]、Mn基[10]及Au基[11]等。

采用钎焊技术连接的铝合金复杂异质构件,凭借其良好的耐腐蚀性、优异的导热与导电性能等[12],已广泛应用于Cu/Al[13]、SiCp/Al[14]、Fe/Al[15]、Ti/Al[16]等材料的连接。然而,传统Al基钎料仍存在熔点偏高、润湿性与接头强度不足等问题。为突破这些瓶颈,当前研究聚焦于通过合金成分设计优化其综合性能。例如,在Al基钎料中添加Cu、Zn、Ge等元素可有效降低熔点,但Cu、Ge等元素的引入易形成Al-Cu、Si-Ge等脆性金属间化合物(intermetallic compounds, IMCs),导致钎料脆性增大、加工成形困难,限制了其工程应用[17]。针对高性能钎料脆性大、难成形的问题,采用原位合成法制备复合钎料成为一种有效解决途径。该方法在钎焊过程中通过不同物质或元素之间的原位反应,在钎缝内形成弥散分布的新相或增强相,不仅能够抑制脆性相生长,还可显著提升接头力学性能。目前,基于原位合成理念的钎料形式主要包括药芯药皮钎料、层状复合钎料与膏状复合钎料等[18],不仅克服了脆性钎料的成形难题,也简化了制备流程,有利于降低生产成本。

为获得高性能、高可靠性的钎焊接头,必须对工艺进行优化,并深入揭示钎焊过程中微观组织,特别是脆性金属间化合物与氢气孔缺陷的形成与生长机制。这对调控接头组织、提升力学性能至关重要。然而,传统快淬截断与静态二维表征技术常常忽略动态信息变化,造成生长细节缺乏[19]。基于同步辐射X射线的二维成像与微观断层扫描技术为获取动态变化、深入揭示钎焊机制提供一种有效的表征方法[20]

本文将从Al基钎料合金成分设计、复合钎料优化设计、脆性化合物与气孔缺陷的原位研究等方面,综述了不同Al基钎料的成分研制与性能优化,以及复杂形态脆性化合物的形成、生长与形态演变机制,进而对高性能Al基钎料的未来发展趋势进行展望。

1 合金成分设计

铝合金具有密度低、导热性好、耐腐蚀性高及成本较低等优点,在现代工业中应用广泛。将其与其他金属连接,既能结合不同材料的成分与性能优势,也有助于降低整体成本[21]。目前,铝合金钎焊主要采用Al-Si基和Zn-Al基钎料,但其熔点与母材接近,钎焊过程中易导致母材过烧或熔蚀[22]。因此,通过合理的合金成分设计,添加一种或多种合金元素,利用元素间的相互作用,可精确调控钎料的熔点、润湿性、铺展性及其与母材的界面行为,从而优化钎焊接头的微观组织并提升其综合力学性能,以获得高可靠钎焊接头[23]

1.1 Al-Si系钎料成分优化

Al-Si系钎料因其良好的钎焊工艺性和与母材的相容性,成为铝合金钎焊中应用最广泛的材料体系[24]。为优化钎焊接头的综合性能并拓宽应用场景,以往研究主要通过多元合金化的途径对Al-Si钎料进行改性,主要围绕以下几个方向展开:一是通过添加合金元素以降低钎料熔点,扩大钎焊工艺窗口;二是通过微合金化细化微观组织,以改善力学性能[25];三是引入特定活性元素以改善其在难焊材料(如陶瓷、复合材料)上的润湿性与界面结合。

1.1.1 多元共晶成分降低熔点

传统Al-Si钎料的熔点较高,与多数工业铝合金的固相线温度接近,这极大地限制了其工艺窗口与应用范围。为降低钎料熔点,通常在Al-Si钎料中添加Cu[26]、Ni[27]、Ge[28]、Zn[29]等元素,如图1所示。Chuang等[26]研制了低熔点Al-Si-Cu钎料,发现随着Cu质量分数从0 %增加至15%,钎料液相线温度由593 ℃降至548 ℃,熔点显著降低,如图1(a)所示。Luo等[30]在Al-Si钎料中复合添加Cu和Ni,发现随二者含量增加,钎料熔点不断降低(图1(b)),这是由于Cu与Ni元素抑制了Al-Si二元共晶反应,而Ni可缩小熔化区间、细化组织,并改善润湿性[31]。Niu等[32]研究了Ge元素对钎料熔点的影响,发现当Ge质量分数从0%增加至30%时,钎料熔点由592 ℃下降至519 ℃,如图1(c)所示。Tsao等[33]在Al-Si钎料中添加Cu与Zn元素,使钎料熔点显著降低,液相线与固相线温度分别降至535 ℃与468 ℃(图1d)。此外,向Al-Si-Ge钎料中添加Zn元素不仅能进一步降低熔点,还能提升其在纯铝表面的润湿性与铺展面积[34]。因此,添加Cu、Ni、Ge、Zn等三元及以上共晶元素可显著降低Al-Si钎料熔点,并改善其润湿性与微观组织。

图 1 AlSi-xCu钎料、AlSi-xCu-yNi钎料、Al-Si-xGe钎料与AlSi-xCu-yZn钎料的液相线和固相线温度 Fig. 1 Liquidus and solidus temperatures of the AlSi-xCu, AlSi-xCu-yNi, Al-Si-xGe, and AlSi-xCu-yZn brazing filler metals
1.1.2 稀土元素细化微观组织

在传统Al基钎料中添加稀土元素(如Sr[35]、Y[36]、La[37]、Ce[38])可细化晶粒、改善润湿性,进而提升钎缝力学性能。Du等[39]研究了Sr对Al-Si-Cu钎料的影响,发现当Sr质量分数为0.08%时,针状Al-Si共晶与块状初晶Si被细化为颗粒或短棒状;但Sr过量则会导致Si相粗化及孔隙率增大(图2a)。钎料剪切强度随Sr质量分数呈先增后减趋势,该变化规律与晶粒尺寸变化密切相关。Dai等[40]发现在Al-6.5Si-42Zn合金中加入0.09%的Sr元素可细化α-Al晶粒,并促使针状Si相转变为细小的纤维状。Yu等[41]在Al-Si-Cu钎料中添加Y,发现当Y质量分数为0.3%时,初生Si相、α(Al)相及树枝状Al2Cu相均明显细化(图2(b)),剪切强度达到峰值。Wang等[42]在Al-Si钎料中添加La与Ce元素,发现可细化组织、促进成分均匀分布,其向母材中的扩散进一步增强了接头强度。因此,适量添加稀土元素可有效细化钎料组织、改善界面结合,但过量添加易导致组织粗化与性能下降,故需严格控制添加含量。

图 2 稀土元素Sr和Y对Al基钎料微观组织的影响 Fig. 2 Effect of rare earth elements Sr and Y on the microstructure of Al-based brazing filler metals
1.1.3 活性元素增强润湿

Al基钎料在陶瓷、SiP/Al复合材料表面的润湿性较差,制约其焊接效果。为此,常在其中添加Ti、Zr、Cr等活性元素以改善其润湿性与连接性能。Zhang等[43-44]在Al-Si钎料中添加Ti,发现Ti可减少中间层液相排出,消除界面间隙;而少量Ti偏聚至陶瓷表面并形成多元氧化物薄层,从而显著提升润湿性。Li等[45]在Al-Si-Ni-Cu钎料中添加微量Er与Zr元素,使晶粒尺寸约减小一半,Al-Cu金属间化合物由长条状转为短棒状(图3(a)),尺寸由20 μm降低至10 μm。Gao等[46]采用薄带状Al-Si-Cu-Ni-Ti钎料成功钎焊了铝基复合材料,发现Ti元素可抑制位错运动,并在界面处形成少量金属间化合物,从而提高接头剪切强度;但Ti含量过高会促进脆性相形成,导致强度下降(图3(b))。因此,添加Ti、Zr等活性元素可显著增强Al基钎料的润湿性,并通过细化组织、调控界面反应提升接头性能,但其添加量需严格控制以避免过量脆性相形成。

图 3 Al-10Si-2Ni-6Cu-0.2Er-0.2Zr钎料钎焊Cu/Al接头截面微观组织与AlSiCuNi-xTi钎料接头剪切强度 Fig. 3 Microstructure of the cross-section of Cu/Al joint brazed with Al-10Si-2Ni-6Cu-0.2Er-0.2Zr brazing filler metal, and the shear strength of AlSiCuNi-xTi brazing filler metal joints
1.2 Zn-Al系钎料成分优化

Zn-Al钎料因其熔化温度显著低于Al-Si系钎料(通常在400~500 ℃),为铝合金钎焊提供了更低的工作温度[47]。然而,其中较高的Zn质量分数易在钎焊过程中引起铝合金基体腐蚀,成为限制其接头强度与可靠性的主要瓶颈[48]。为克服这一问题,研究主要通过两种途径进行优化:一是添加Cu、Si等元素,直接提升钎料的耐腐蚀性与接头强度;二是引入微量Ti、Ce、Zr等,细化微观组织并抑制脆性相过度长大,从而改善接头的综合力学性能。

1.2.1 微量添加提升耐腐蚀性能

Kolenak等[49]在Zn-Al钎料中添加Cu,发现添加Cu可形成CuZn4与Al2Cu等金属间化合物,有利于强化接头。同时,Cu质量分数的增加降低了Zn的比例,减轻了Al母材向钎缝的溶解,从而提升了钎料的耐腐蚀性。Yu等[50]通过盐雾试验,发现添加Si可减小接头表面腐蚀的尺寸与深度,如图4(a)所示。分析腐蚀产物,可知点蚀始于富Zn区域。另外,添加Si元素改变了共晶形貌,抑制了Zn的反应活性,从而提高了耐腐蚀性;随着Si质量分数增加,接头耐腐蚀性得到提升。未添加Si的钎料经6 d盐雾腐蚀后剪切强度大幅下降,而随着Si元素含量增加,强度下降趋势明显减缓(图4b)。赵月[51]通过合金元素Ge调控药芯Zn-2Al钎料的微观组织与耐腐蚀性(图4c),发现Ge的添加抑制了钎料的点蚀速率,减少了钎料中的微腐蚀孔洞,减轻了晶界处位错塞积与应力集中,阻碍了裂纹的扩展,使钎料断裂由脆性沿晶断裂向韧性断裂转变,抑制了药芯Zn-2Al钎料的脆化。因此,在Zn-Al钎料中添加Cu、Si、Ge可分别通过抑制富Zn区腐蚀、形成强化相等方式,显著提高接头的耐腐蚀性能与强度。

图 4 ZnAl-xSi钎料盐雾腐蚀后微观组织、接头强度及ZnAl-xGe钎料腐蚀形貌 Fig. 4 Microstructure and joint strength of ZnAl-xSi brazing filler metals after salt spray corrosion, and corrosion morphology of ZnAl-xGe brazing filler metals
1.2.2 微量元素细化组织与调控性能

在Zn-Al钎料中添加Ti、Sr、Ce、Zr、La等微量元素可有效细化微观组织,并提高接头剪切强度。Ji等[52]通过添加Ti使粗大条状的Al2Cu脆性化合物转变为针状,同时减小了界面CuZn与Al2Cu化合物的平均厚度。这主要归因于高熔点的Al3Ti颗粒抑制了界面处Zn、Al、Cu原子的扩散,从而限制了金属间化合物层的过度生长,使组织细化且尺寸均匀,进而提升接头性能。Feng等[53]发现Ce对钎料熔点影响较小,但能显著改善组织均匀性(图5a);适量的Ce可细化晶粒,而Ce质量分数超过0.25%时则会在断口形成脆性金属间化合物(图5b),导致力学性能下降。此外,适量添加Zr可细化η-Zn枝晶,但过量的Zr会促使形成Fe4Al13脆性相,降低接头质量。因此,适量添加Ti、Ce、Zr等能通过细化组织与抑制脆性相过量生长,提升Zn-Al钎料与接头性能,但其含量需精确控制,过量反而会导致脆性增加与性能劣化。

图 5 Zn-22Al-xCe钎料的微观组织与接头断口形貌[53] Fig. 5 Microstructure of Zn-22Al-xCe brazing filler metal and joint fracture morphology[53]
2 Al基复合钎料优化设计

传统钎焊工艺多采用实心钎料配合粉末或膏状钎剂,存在钎剂量控制困难、易吸潮失效、环境污染及焊接一致性差等问题[54]。随着陶瓷/金属、铝/钢等异质材料连接需求的增加,接头残余应力大、易形成脆性相、润湿性差等问题也日益突出。为此,将钎料与改性剂、钎剂或功能相结合,通过材料设计与结构创新开发的复合钎料逐渐发展起来[55],旨在实现成分与性能的精准调控、改善润湿铺展行为、抑制有害界面反应、缓解残余应力,可有效克服传统钎焊工艺的局限性,为异质材料高质量连接提供了可靠路径。目前常见的复合钎料形式包括:层状复合钎料与母材表面镀层[56]、集成了钎剂的药芯及药皮钎料[57],以及可精确定量配比的复合钎焊膏[58]。这些形式从不同角度提升了钎焊接头的力学性能、可靠性及工艺稳定性,为先进连接制造提供了重要材料支撑。

2.1 层状复合钎料与表面镀层

采用层状复合钎料与表面镀层技术,可通过结构调控抑制脆性相生长,优化微观组织状态并改善钎料的润湿性能,从而提升异质材料的连接性能。Lee等[59]制备出Al-Si/Al-Mn/Al-Si层状复合钎料,通过在中间Al-Mn合金中添加Zn,调控了退火与冷轧过程中再结晶组织尺寸与分布,有效提升了接头的耐腐蚀性能。Cao等[60]在母材表面镀Zn,钎焊时镀Zn层发生熔化,增强了Al基钎料的润湿性。Wang等[61]在陶瓷表面镀Ni层,将陶瓷/金属连接转化为金属/金属界面连接,实验表明化学镀Ni层显著提高了钎料润湿性,并使Ni膜与SiC颗粒紧密结合。在铝/钢异质材料连接中,在钢侧镀Ni层可调控接头组织并改善力学性能。从图6中可知,未镀Ni层的接头处形成约10 μm厚的Fe(Al,Si)3金属间化合物层,而镀Ni层的接头则生成更致密的Al3Ni相[62],这是由于Ni层在钎焊过程中溶解并向Al侧扩散,过饱和的Ni在冷却时析出为Al3Ni相,使接头强度提高了约20.3%,显著增强钎料润湿性与界面结合强度。因此,开发层状复合钎料与表面镀层通过调控界面结构与反应,能有效抑制脆性相过量生长,从而提升接头性能与可靠性。

图 6 Ni镀层对钎焊接头微观组织的影响[62] Fig. 6 Effect of Ni coating on microstructure of brazed joints[62]
2.2 药芯与药皮钎料

传统钎焊工艺常在钎料表面涂抹膏状/粉末钎剂,这不仅增加焊前工序,也影响工艺稳定性。药芯钎料通过将钎剂按比例封装于钎料内部,显著提高了工艺稳定性,并减少了过多钎剂挥发带来的污染。药芯钎料主要分为无缝和有缝两种类型,其结构示意如图7(a)所示[63],可通过调整钎料成分或钎剂与合金粉进行混合,进而调控钎缝组织,优化接头力学性能。Fattahi等[64]制备了含纳米石墨烯的复合钎料,发现随着石墨烯含量增加,钎缝组织由枝晶转变为细小等轴晶,主要归因于石墨烯促进了晶粒细化与应变硬化作用,提升了钎焊接头的抗拉强度与显微硬度。Huang等[65]研究了TiCp/Al-5Mg复合钎料,发现TiC颗粒均匀弥散于钎缝中,细化了α-Al2O3晶粒;随着TiC含量增加,钎缝应力腐蚀敏感性降低,力学性能得到提高。Cai等[66]采用Al-Si药芯钎料钎焊Al/Cu异质接头,在钎缝中未发现微裂纹与空洞,钎料在铝板上的润湿性随温度度升高先增后减;经分析接头断口,发现其断裂主要为解理断裂与沿晶断裂,裂纹多出现在Al2Cu与α-Al相之间,如图7(b)所示。因此,药芯与药皮钎料显著改善了工艺稳定性与环保性,结合合金粉添加与颗粒增强等复合化设计,可有效调控钎缝组织并提升接头强度与韧性。

图 7 药芯钎料结构示意图及钎焊接头断口形貌 Fig. 7 Schematic diagram of flux-cored solder structure and fracture morphology of brazed joint
2.3 膏状复合钎料

传统钎焊过程钎料与钎剂离散使用,存在用量控制难与污染环境等问题;有缝药芯焊丝易吸潮漏粉,无缝药芯焊丝成本高且易飞溅;药皮焊丝则存在涂层易脱落、防潮性差等缺点。为适应绿色制造与自动化生产趋势,开发可精确定量、高效节能的膏状复合钎料成为行业重要需求。Sheng等[67]采用超声气体雾化法制备了3种Al-Si-Cu-Zn-Y基钎焊粉(BA1、BA2、BA3),其组织较铸态组织发生明显细化(图8a),且成分影响较小,配合钎剂可获得质量较好的接头。李秀朋等[68]通过热压烧结将Al88Si粉与钎剂制成自钎剂钎料环,简化了制造工艺并提了高效率。Fei等[69]在保护气氛下制备了粉末冶金铝硅钎料(PM),其抗湿性明显优于普通粉末钎剂与有缝药芯焊丝(SFC)。SFC受潮后接头气孔增多,出现粗大初生Si相,而PM钎焊接头无明显气孔与粗大相(图8b),因而强度更高。此外,在潮湿环境中PM钎料铺展面积保持稳定,而SFC则下降约20%。因此,膏状复合钎料合金粉末具有成本低、钎剂可定量控制、适于自动化生产、储存稳定性好及连接质量高等优势,是推动钎焊工艺向绿色、精准、高效方向发展的重要材料形式。

图 8 铸态和粉末Al-Si-Cu-Zn-Y钎料的微观组织与SFC、PM钎料钎焊界面微观组织 Fig. 8 Microstructure of as-cast and powder metallurgy Al-Si-Cu-Zn-Y filler metals, and interfacial microstructure of joints brazed with SFC and PM filler metals
3 脆性化合物与氢气孔缺陷演化机制原位研究

为提升钎料润湿性及钎焊接头的力学性能,往往在钎料中添加Cu、Ni等合金元素,在加热与冷却过程中易形成Al2Cu与Al3Ni等不规则形态脆性金属间化合物。同时,铝熔体加热过程中易吸氢,并在凝固过程中析氢,易形成氢气孔缺陷,对接头力学性能产生重要影响。因此,研究脆性化合物与气孔缺陷的形成、生长与形态演变机制对钎料与钎焊接头组织性能调控至关重要。

3.1 脆性化合物生长与形态演变

板条状与中空状Al3Ni脆性化合物是铝钎料与钎缝中常见的不规则形态化合物。Ding等[70]利用同步辐射X射线成像技术发现中空状Al3Ni脆性化合物基于螺型位错形成,沿[001]的择优取向生长,位错中心生长速度大于外部边缘生长速度,呈现明显各向异性的板条状。当畸变能大于内表面能时,形成中空状Al3Ni脆性化合物,且内部空心形态均匀。当内外部半径比值增大时,形态发生急剧变化,空心形态从规则形态转变为不规则形态,如图9(a)所示。Zhang等[71]通过同步辐射X射线微观断层扫描技术与调控冷却速率,发现随着冷却速率增加,Al3Ni脆性化合物从小平面的板条状与中空状转变为非小平面的枝晶状,且枝晶臂末端呈现V形小平面生长特征(图9b),非小平面Al3Ni枝晶的生长方向则从[011]转变为[010]。对于具有分枝结构的非规则形态小平面Al2Cu脆性化合物,Ding等[72]通过原位研究发现其Al2Cu主枝与侧台阶呈垂直关系,且在交界处存在部分晶体合并现象,这是由于新形成晶粒沿对角线方向持续增殖与生长所致,如图9(c)所示。Song等[73]重构了其三维形态为等轴-棱柱结构,发现在x-z平面内呈近等轴状生长,而在y方向上则呈现棱柱状生长,且Al2Cu分支呈小平面状且棱角分明(图9d),在初期分支长度几乎呈线性增长,随后逐渐减缓。另外,随着冷却速度增加,复杂形态非小平面的海藻状、枝干状与非规则近枝晶状Al2Cu脆性化合物相继形成[74]。因此,同步辐射X射线二维成像与微观断层扫描技术可渲染重构脆性化合物的复杂三维形态,深入揭示了非规则形态脆性化合物的生长与形态转变机制,有利于实现钎料与钎焊接头组织调控。

图 9 Al3Ni及Al2Cu化合物的同步辐射二维实时生长图像及三维形态 Fig. 9 Two-dimensional in-situ growth images and three-dimensional morphology of Al3Ni and Al2Cu compounds obtained by synchrotron radiation
3.2 氢气孔缺陷演化机制

丁宗业等[75]利用同步辐射X射线成像技术,发现加热过程中氢气孔存在异质形核,发生在枝晶间与化合物间的交汇处,以及双层表面膜的形核机制。另外,氢气孔存在向上迁移与无定向跳跃的两种运动行为。在加热过程中,单个气泡的生长遵循随机生长模型;而群体气泡的尺寸分布由高斯分布向Lifshitz-Slyozov-Wagner(LSW)扩散控制分布转变[76]。Sun等[77]发现凝固过程中氢气泡的生长与Al3Ni脆性金属间化合物存在相互作用,在化合物作用下气泡生长过程可分为3个阶段:自由生长阶段、加速生长阶段和收缩阶段,如图10(a)所示。其中,自由生长符合随机模型,加速生长主要归因于界面处氢浓度梯度的增加,而负的浓度梯度则导致气泡的收缩。Lu等[78]认为在加热过程与脆性化合物作用下氢气孔形状由不规则状逐渐演变为近球形与球形(见图10b),且气孔的生长行为主要与氢浓度梯度密切相关,同时氢气孔会加速脆性金属间化合物的溶解,使其溶解过程遵循Logistic模型。因此,通过原位研究可深层次揭示钎料与钎焊加热和凝固过程中氢气孔的形核、生长、运动与形态转变机制,为去除气孔与夹渣缺陷、制备高洁净铝钎料与高质量钎焊接头提供重要理论支撑。

图 10 凝固及加热过程中金属间化合物对氢气泡生长行为的影响 Fig. 10 Influence of intermetallic compounds on the growth behavior of hydrogen bubbles during solidification and heating
4 总结与展望

针对铝合金复杂与异质构件钎焊过程中存在易形成脆性化合物[79-80]、润湿性不佳[81]、残余应力大[82-83]等问题,通过对Al基钎料进行合理的合金成分设计,同时开发多材料体系与结构创新的复合钎料,能够有效降低其熔点并优化润湿铺展性能[84],抑制脆性化合物过量并细化组织,显著缓解接头残余应力[85],提升钎缝力学性能,达成高可靠连接。借助同步辐射X射线二维成像与微观断层扫描技术,能够实时研究微观组织与缺陷的动态演变,深入揭示复杂形态化合物与氢气孔的形核与生长动力学机制。

面向新型材料不断涌现及铝合金构件加工与服役环境日益极端化,传统Al基钎料与钎焊技术已难以满足需求,面临新的挑战;同时,基于以往研究形成的机制与理论模型已不再适用。因此,高效开发出性能更加优异、相匹配的Al基钎料及应用技术,以适应自动化与智能化发展趋势,已成为当务之急。结合未来技术发展趋势,Al基钎料的未来发展将主要集中在以下几个方向:

(1)对于新型Al基钎料的研制,以往主要采用“试错法”,研发周期长、成本高;而机器学习与人工智能技术的融合为钎料成分−组织−性能的逆向设计与快速筛选提供了革命性工具[86]。通过构建包含成分、工艺、微观组织特征(相组成、晶粒尺寸、金属间化合物形态等)及宏观性能(润湿铺展性、接头强度、耐蚀性等)的高通量数据库,并利用神经网络、随机森林等算法建立其间的映射与预测模型,可加速新型Al基钎料的成分设计与工艺优化,从而实现对钎料性能的定向调控与定制化开发。

(2)对于新型Al基钎料与极端条件下(激光焊、超高低温、超高压、强腐蚀、强磁场等)的钎焊理论和力学模型,传统静态表征与推断导致动态信息缺乏,限制了理论模型的发展。基于同步辐射X射线的超快速成像、衍射配套装备及相关融合技术,可实现组织、缺陷与应力的同时在线表征,深入揭示极端条件下钎焊理论及相变和应变演化模型,为开发相应新型技术奠定基础。

(3)在钎焊过程自动化与智能化控制方面,将传感器技术、机器视觉、工业互联网与人工智能深度集成,实现对钎焊温度场、钎料/钎剂添加量的精确闭环控制;通过过程数据实时采集与分析、在线预测与调控,可实现焊接缺陷的即时诊断与工艺参数的自适应优化。

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